JP5871935B2 - Radiation curable poly (isobutylene) adhesive copolymer - Google Patents

Description

(Cross-reference of related applications)
This application claims the benefit of US Patent Application No. 13/169573, filed June 27, 2011, and the benefit of US Provisional Patent Application No. 61 / 388,283, filed September 30, 2010. , The disclosures of which are hereby incorporated by reference in their entirety.

(Field of Invention)
The present invention relates to pressure sensitive adhesives and adhesive sealants prepared from isobutylene copolymers, and tape articles prepared therefrom. The pressure-sensitive adhesive is characterized by exhibiting an excellent balance of adhesiveness and sticking characteristics, and excellent adhesion to a substrate having a low surface energy.

  Pressure sensitive tape exists virtually everywhere in the home and the workplace. In its simplest configuration, the pressure sensitive tape comprises an adhesive and a backing, and the overall structure is tacky at the temperature of use and can be applied to various substrates with only moderate pressure to form a bond. Glue. In this manner, the pressure sensitive tape constitutes a complete and self-contained fastening system.

  According to the Pressure Sensitive Tape Council, pressure sensitive adhesives (PSAs) are known to have the following properties: (1) strong and permanent tackiness, (2) tackiness under finger pressure, (3 ) Sufficient holding force on the adherend or substrate, and (4) Sufficient sticking force to remove cleanly from the adherend. Materials that have been shown to function well as PSA include polymers that are designed and formulated to exhibit the required viscoelastic properties and provide the desired balance of tack, peel adhesion, and shear retention. PSA is characterized by exhibiting normal tack at room temperature (eg, 20 ° C.). PSA does not embrace the composition only by stickiness or adhesion to the surface.

These requirements are generally described in A.C. V. Pocius in Adhesion and Adhesives Technology: An Introduction, 2 nd Ed. , Hanser Gardner Publication, Cincinnati, OH, 2002, evaluated by a test method designed to measure adhesive strength, adhesive strength (peel strength) and cohesiveness (shear retention) individually . Overall, these measurements constitute a balance of properties often used in characterizing PSA.

  With the increasing use of pressure sensitive tape over the years, the level of performance required is higher. For example, the shear holding force, which was originally intended for application to support a moderate load at room temperature, has been greatly increased to accommodate various uses from the viewpoint of operating temperature and load. The so-called high performance pressure sensitive tape is a tape capable of supporting a load at a high temperature for 10,000 minutes. Increased shear retention is usually achieved by cross-linking PSA, but considerable care must be taken to maintain a high degree of adhesion and adhesion in order to maintain the aforementioned property balance. is there.

Currently, various pressure sensitive adhesive (PSA) materials are available, such as natural or synthetic rubbers, block copolymers, and acrylate polymer compositions. A desirable balance of adhesion and cohesion is central to all PSA. In many cases, this balance is achieved by optimizing physical properties such as glass transition temperature and elastic modulus of the acrylic acid elastomer. For example, the glass transition temperature (T _g ) or modulus of elasticity of an elastomer is too high and exceeds the Durquist standard for tackiness (storage at 3 × 10 ⁶ dynes / cm ² at room temperature and 1 Hz vibration frequency) Elastic modulus), the material is no longer sticky and is not useful as a PSA material. In such cases, often, the use of high resin polymer having T _g in the low molecular weight low T _g in (tackifiers) or low molecular weight polymer (plasticizer), T _g and modulus PSA Is adjusted to the optimum range.

  The adhesive (co) polymer of the present disclosure comprises a) an isobutylene copolymer having pendant free radical polymerizable ethylenically unsaturated groups, b) a tackifier, and c) a cross-linking agent. In one aspect, the pressure sensitive adhesive comprises an internally polymerized reaction product of isobutylene and at least one monomer having pendant free radical polymerizable ethylenically unsaturated groups.

The pressure sensitive adhesives of the present disclosure provide tack, peel adhesion, shear retention in the desired balance and further comply with Dalquist standards, i.e. adhesives at application temperature (typically room temperature) The elastic modulus of is less than 3 × 10 ⁶ dynes / cm at a frequency of 1 Hz.

  In some embodiments, a hot melt adhesive composition is provided that is applied from a melt to a substrate. Such hot melt adhesive compositions are substantially free of solvents. Hot melt adhesives are versatile and are widely used in industrial applications such as bookbinding, cardboard boxes, plastic parts, and wooden articles, among others. They are generally 100% solid adhesives at different application temperatures from about 150 to about 180 ° C.

  In recent years, the use of olefinic thermoplastics having a low surface energy (for example, polyethylene, polypropylene, ethylene propylene diene monomer rubber (EPDM)) has increased remarkably in the automobile, paint, electrical appliance and electronic equipment markets. The advantages of the new material include affordable cost, easy processability, and excellent mechanical properties. However, this trend creates challenges with respect to bonding adhesives to these low energy surfaces.

When considering adhesive tapes, pressure sensitive adhesive (PSA) tapes are the easiest to use, but for the most part pressure sensitive adhesives do not adhere well to low surface energy substrates. Furthermore, most PSA is not suitable for use requiring good internal (sticking) strength at elevated temperatures. For example, rubber-resin PSA tends to soften and deteriorate during heating. Styrene-containing block copolymers based PSA also styrene has a low T _g, therefore, to soften the moderate heating, it does not retain good internal strength when heated. Currently, bonding to low surface energy surfaces is accomplished by priming the substrate with a polar liquid followed by application of PSA. Even after this two-step process, existing PSAs do not meet customer requirements. There is a need to develop a primerless LSE PSA that is competitively priced but still has the most optimized properties.

  Recently, polyisobutylene (PIB) has been considered as an attractive material for low surface energy (LSE) bonding applications due to its superior adhesion properties to olefinic thermoplastics. In addition, the excellent moisture and oxygen barrier properties of PIB suggest that PIB-based materials have potential use in electronic and photovoltaic encapsulation applications. Despite its beneficial properties, the low tack strength of the material limits its use for high shear applications. Another possible application for PIB-based materials is in the medical adhesive field. Most acrylate-based PSAs are not suitable for medical applications because acrylate PSAs tend to emit toxic vapors at elevated temperatures. Acrylate-based PSA typically contains monomeric materials that emit an odor that renders acrylate PSA tapes generally unsuitable for medical use, even at normal room temperature. Polyisobutylene PSA is often used for medical applications because they are physiologically inert, but again, they tend to be deficient in internal strength.

  The adhesive composition of the present disclosure can be adhered to a variety of substrates, including low surface energy (LSE) substrates, within a wide temperature range and can provide good adhesive strength and retention properties Pressure and hot melt adhesive compositions are provided. The adhesive composition is easily handled and is environmentally friendly due to the low volatile organic compound (VOC) content (solvent etc.). The adhesive composition of the present disclosure further provides pressure sensitive adhesive articles such as adhesive tapes and sealants.

  The adhesive copolymer includes an isobutylene copolymer having pendant free radical polymerizable ethylenically unsaturated groups, b) a tackifier, and c) a photocrosslinker. In one aspect, the pressure sensitive adhesive is internally polymerized with isobutylene and at least one monomer having pendant free radical polymerizable ethylenically unsaturated group (s), including alkenyl, allyl, and vinyl groups. Reaction products.

（式中、Ｑは多価、好ましくは二価連結基であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基であり、Ｒ^７はＨ又はＣＨ_３である）である。より具体的には、イソブチレンコポリマーは、式；

（式中、ａは少なくとも２０であり、ｂ及びｃのうちの少なくとも１つは、少なくとも１であり、Ｑは多価連結基であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基である）であってもよく、又は

（式中、ａ及びｄは少なくとも１であり、好ましくはａは少なくとも２０であり、ｄは少なくとも１であり、Ｒ^７はＨ又はＣＨ_３であり、Ｑは多価連結基であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基である）であってもよい。 Monomers having pendant free radical polymerizable ethylenically unsaturated groups may be derived from halogenated butyl rubber and have the general formula:

Wherein Q is a polyvalent, preferably a divalent linking group, Z is a pendant free radical polymerizable ethylenically unsaturated group, and R ⁷ is H or CH ₃ . More specifically, the isobutylene copolymer has the formula:

Wherein a is at least 20, at least one of b and c is at least 1, Q is a polyvalent linking group, and Z is a pendant free radical polymerizable ethylenically unsaturated group. ), Or

Wherein a and d are at least 1, preferably a is at least 20, d is at least 1, R ⁷ is H or CH ₃ , Q is a multivalent linking group, Z is A pendant free radical polymerizable ethylenically unsaturated group).

（式中、Ｒ^１は多価アルキレン又はアリーレンであり、Ｘ^１は−Ｏ−、−Ｏ_２Ｃ−、−ＮＲ^４−（式中、Ｒ^４はＨ又はＣ_１〜Ｃ_４アルキルである）、又は−Ｒ^２−Ｃ（Ｒ^５）＝ＣＲ^５ _２であり、Ｒ^２は多価飽和又は不飽和アルキレン又はアリーレンであり、各Ｒ^５は、Ｈ又はＣ_１〜Ｃ_４アルキルから独立して選択され、Ｒ^５基のうちのいずれか２つは、一緒になって炭素環を形成し得、ｑは１又は２であり、ｒは１〜５である）であってもよい。 It will be appreciated that for the copolymers of Formulas I and II, the monomer unit having the subscript “a” is an internally polymerized isobutylene monomer unit. The polymerizable Z group is a non-conjugated ethylenically unsaturated group selected from alkenyl, alkynyl, and allyl groups, preferably not a vinyloxy group, eg, CH ₂ ═CHO— or (meth) acrylate group . The -QZ moiety is represented by the formula:

(Wherein R ¹ is a polyvalent alkylene or arylene, and X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C ₁ -C ₄ alkyl) , or ^-R 2 ^-C (R 5) = a ^CR _{5 2,} ^{R 2} is a polyvalent saturated or unsaturated alkylene or arylene, each ^{R 5} is independently H or _C 1 -C ₄ alkyl And any two of the R ⁵ groups may be taken together to form a carbocycle, q is 1 or 2, and r is 1-5.

の化合物（式中、Ｒ^１、Ｒ^２、Ｒ^５、及びｒは、先に定義されるとおりである）を提供することが理解されよう。 With respect to the above formula, when X ¹ is —NR ⁴ —, R ⁴ may be selected as —R ² —C (R ⁵ ) = CR ⁵ ₂ , wherein:

It will be appreciated that the following compounds are provided: wherein R ¹ , R ² , R ⁵ , and r are as defined above.

In certain preferred embodiments, the —QZ moiety may be of the formula —R ¹ — [X ¹ — (R ² —CH═CH ₂ ) _q ] _r , ie, all R ⁵ groups are H. Yes, q is 1 or 2, and r is preferably 1.

  Further, with respect to Formulas I and II, the subscripts “b” and “c” or “d” are selected such that the copolymer contains 1-20% by weight of each monomer unit, for example, b and c are , -QZ monomer units such that they contain 1-20% by weight of copolymer.

  Copolymers of formulas I and II are generally obtained by nucleophilic substitution of commercially available halogenated PIBs, including halogenated poly (isobutylene-co-methylstyrene), halogenated poly (isobutylene-co-isoprene). Prepared. Alternatively, the non-halogenated PIB-based material may be halogenated and then subsequently replaced. The halogen moiety in these materials allows for the introduction of pendant ethylenically unsaturated groups.

The reaction scheme comprises a substitution reaction with a “nucleophilic ethylenically unsaturated compound”, an organic compound having at least one nucleophilic functional group and at least one ethylenically unsaturated group (hereinafter “nucleophilic unsaturated compound”). Including. The unsaturated group may be alkenyl, including vinyl, allyl, or allyloxy, and the nucleophilic functional group may be an amino, carboxyl, or hydroxy group. Preferably, the unsaturated group, vinyloxy group, for _example, is not a CH 2 = CHO- or (meth) acrylate groups. Since carboxyl groups are less nucleophilic than hydroxyl or amine, nucleophilic substitution may be enhanced by using a phase transfer catalyst such as tetra-n-butylammonium hydroxide.

  In some embodiments, the nucleophilic unsaturated compound is a polyunsaturated compound having a hydroxyl group and one or more unsaturated groups including terpene alcohols and acids derived from plant material. In other embodiments, the nucleophilic unsaturated compound consists of a carboxy group having one or more unsaturated groups, such as those carboxy compounds derived from unsaturated fatty acids, such as linoleic acid, linolenic acid, and arachidonic acid. .

  In such embodiments, where the adhesive is derived from terpene alcohol or acid, the present disclosure provides an adhesive composition derived from renewable resources. In such embodiments, the present invention further provides an adhesive article, and the substrate or backing is also derived from renewable resources. Increased prices for oil and associated petroleum derivatives have led to price increases for many adhesive products and destabilization of supply. It is desirable to replace all or part of the petroleum-based raw material with one derived from renewable resources such as plants, but this makes it relatively inexpensive and thus economical and social Because it is beneficial to. Therefore, the need for such plant-derived materials is increasing.

  Terpene alcohols and acids are a well-defined class of compounds based on five-carbon isoprene units and having at least one hydroxyl or carboxylic acid group that can be primary, secondary, or tertiary. Terpene alcohols and acids are plant-derived acyclic, monocyclic, bicyclic, or tricyclic, monoolefinic or polyolefinic unsaturated alcohols containing 10 to 40 carbon atoms. Terpene alcohols and acids are structurally similar to terpene hydrocarbons, except that their structure also contains some hydroxyl or carboxyl functionality. Terpene alcohols and acids can be found in essential oils and are generally available through commercial sources.

  Examples of unsaturated aliphatic terpene alcohols include geraniol, nerol, citronellol, hydroxycitronellol, linalool, α-terpenol, borneol, isoborneol, terpinen-4-ol, limonen-4-ol, carveol, lavandol, menthol, 8 -P-simenol, cis-pinanol, trans-pinanol, dihydromyrsenol, myrcenol, dihydrolinalool, isomenthol, neomenthol, isopulegol, trans-p-menthane-3,8-diol, isoborneol, globrol, cedro, Menthol, sobrerol, umbellol, nerolidol, pinanediol, farnesol, fenquil alcohol, eugenol, phytol, isophytol, phyta Triol, berbenol, trans-pinocarbeol, carveol, nopol, cimenol, piperitol, anethole, camphenol, limonenol, abiethyl alcohol, hydroabiethyl alcohol, 2-hydroxy-methyl-5-norbornene, 6,6-dimethylbicyclo (3,1,1) -2-heptene-2-ethanol, and combinations thereof. As will be appreciated, the corresponding amine or carboxyl substituted terpenes may also be used.

（式中、
Ｘ^１は−Ｏ−、−Ｏ_２Ｃ−、−ＮＲ^４−（式中、Ｒ^４はＨ又はＣ_１〜Ｃ_４アルキルである）、又は−Ｒ^２−Ｃ（Ｒ^５）＝ＣＲ^５ _２であり、Ｒ^２は多価飽和又は不飽和アルキレン又はアリーレンであり、各Ｒ^５は、Ｈ又はＣ_１〜Ｃ_４アルキルから独立して選択され、Ｒ^５基のうちのいずれか２つは、一緒になって、多くのテルペンアルコールにおいて見出されるような炭素環を形成し得、ｑは１又は２である）が挙げられる。好ましくはｑは１よりも大きい。得られた求核ポリ不飽和化合物は、コポリマー上の複数の架橋部位の追加を可能にする。 In some embodiments, useful unsaturated nucleophilic compounds include those of the formula:

(Where
X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C _{1 to} C ₄ alkyl), or —R ² —C (R ⁵ ) ═CR ⁵ _2. R ² is polyvalent saturated or unsaturated alkylene or arylene, each R ⁵ is independently selected from H or C ₁ -C ₄ alkyl, and any two of the R ⁵ groups are Taken together can form a carbocycle as found in many terpene alcohols, q is 1 or 2. Preferably q is greater than 1. The resulting nucleophilic polyunsaturated compound allows the addition of multiple crosslinking sites on the copolymer.

式中、
Ｘ^１は−Ｏ−、−Ｏ_２Ｃ−、−ＮＲ^４−（式中、Ｒ^４はＨ又はＣ_１〜Ｃ_４アルキルである）、又は−Ｒ^２−Ｃ（Ｒ^５）＝ＣＲ^５ _２であり、Ｒ^２は多価飽和又は不飽和アルキレン又はアリーレンであり、各Ｒ^５は、Ｈ又はＣ_１〜Ｃ_４アルキルから独立して選択され、Ｒ^５基のうちのいずれか２つは、一緒になって、多くのテルペンアルコールにおいて見出されるような炭素環を形成し得、ｑは１又は２であり、
Ｘ^２は、ハロゲン化物、及び好ましくは臭化物といった、脱離基であり、
Ｒ^１は、多価アルキレン又はアリーレンである。上のスキームにおいて見られるように、ペンダントフリーラジカル重合性エチレン性不飽和基を有するイソブチレンコポリマーが、求核エチレン性不飽和化合物によるハロゲン化イソブチレンコポリマーの求核置換によって調製される。

Where
X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C _{1 to} C ₄ alkyl), or —R ² —C (R ⁵ ) ═CR ⁵ _2. R ² is polyvalent saturated or unsaturated alkylene or arylene, each R ⁵ is independently selected from H or C ₁ -C ₄ alkyl, and any two of the R ⁵ groups are Together, they can form a carbocycle as found in many terpene alcohols, q is 1 or 2,
X ² is a leaving group such as halide, and preferably bromide,
R ¹ is a polyvalent alkylene or arylene. As seen in the above scheme, an isobutylene copolymer having pendant free radical polymerizable ethylenically unsaturated groups is prepared by nucleophilic substitution of a halogenated isobutylene copolymer with a nucleophilic ethylenically unsaturated compound.

  Compounds of formula III include polyols terminated with mono-, di- or polyunsaturated ethers such as 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, neopentyl Glycol, caprolactone modified neopentyl glycol hydroxypivalate, diethylene glycol, dipropylene glycol, bisphenol-A, trimethylolpropane, neopentyl glycol, tetraethylene glycol, tricyclodecane dimethanol, triethylene glycol, tripropylene glycol, glycerol, penta Examples include erythritol and dipentaerythritol pentaacrylate.

  Useful nucleophilic unsaturated compounds include allyl alcohol, methallyl alcohol, allyloxyethyl alcohol, 2-allyloxymethyl propanol (from dimethylol ethane), and 2,2-di (allyloxymethyl) butanol (tri Hydroxyalkenes (from methylolpropane) and the corresponding amines, in particular diallylamine.

  Copolymers of isobutylene include those in which isobutylene can be copolymerized with another monomer and then modified to include pendant unsaturated groups. Synthetic rubbers include butyl rubber, which is a copolymer of most isobutylene and a small amount of isoprene, such as butyl rubber available under the trade names VISTANEX (Exxon Chemical Co.) and JSR BUTYL (Japan Butyl Co., Ltd.). In some embodiments, the copolymer is substantially homopolymer of isobutylene, which may be subsequently modified to include pendant unsaturated groups, available under the trade names OPPANOL (BASF AG) and GLISSSOPAL (BASF AG). Polymers such as polyisobutylene resins. Copolymers also include copolymers of mostly isobutylene with n-butene or butadiene that may be subsequently modified to contain pendant unsaturated groups. In some embodiments, a mixture of copolymers may be used, i.e., the first polyisobutylene comprises a homopolymer of isobutylene and the second polyisobutylene comprises butyl rubber or the first polyisobutylene. Isobutylene comprises butyl rubber and the second polyisobutylene comprises a copolymer of isobutylene that is subsequently modified. Blends of isobutylene homopolymer and modified poly (isobutylene) are also contemplated.

  The isobutylene copolymer may comprise a random copolymer of isobutylene and modified paramethylstyrene units, the random copolymer containing 1 to 20% by weight of the modified paramethylstyrene units and having a crosslinked structure. This random copolymer is, for example, Exxon Chemical Co. under the trade name EXXPRO series. Examples thereof include MDX90-10 and MDX89-4. The portion of the methyl group at the para position of the paramethylstyrene can be brominated to form a site for subsequent nucleophilic substitution by the compound of formula III. Thus, the crosslinked structure can be formed by techniques described in detail below. In particular, for copolymer MDX90-10, 1.2 mol% paramethylstyrene, contained in the copolymer in an amount of 7.5% by weight, is brominated. For MDX89-4, 0.75 mol% paramethylstyrene, contained in the copolymer in an amount of 5% by weight, is brominated. In addition, bromination of paramethylstyrene and random polymerization between isobutylene and paramethylstyrene for the purpose of producing random copolymers can be performed by known techniques.

  Paramethylstyrene monomer units can also impart heat resistance and strength to the copolymer due to the adhesion and hardness of paramethylstyrene itself. In order to obtain such an effect, paramethylstyrene is preferably included in the copolymer in an amount of more than zero, preferably about 1 to 20 parts by weight, based on the total amount of copolymer. When the amount of paramethylstyrene is less than 1 part by weight, the adhesive strength is insufficient, making it difficult to obtain sufficient adhesion to withstand practical use. On the other hand, when the amount of paramethylstyrene is larger than 20 parts by weight, the flexibility is greatly reduced and the adhesive property as an important characteristic of the adhesive is lost, and hence it is referred to as a pressure sensitive adhesive. Is no longer possible.

  Conventional adhesives do not adhere well to certain substrates, such as certain types of automotive paints and low energy surfaces. Efforts have been made to improve the adhesive properties of the adhesive, i.e. to develop stronger adhesion to these types of surfaces. The tackifying of the base polymer is generally performed. Various types of tackifiers include phenol-modified terpenes, hydrocarbon resins such as polyvinylcyclohexane and poly (t-butylstyrene), and rosin esters such as glycerol esters of rosin and pentaerythritol esters of rosin.

  Various types of tackifiers include rosin, available under the trade names Neuroz (TM), Nutac (TM) (Newport Industries), Permalyn (TM), Staybelite (TM), Foral (TM) (Eastman). Phenol-modified terpenes and rosin esters such as glycerol esters of rosin and pentaerythritol esters of rosin. Hydrocarbon resin tackifiers typically obtained from C5 and C9 monomers with naphtha degradation products, as well as the trade names Piccotac ™, Eastotac ™, Regalrez ™, Regalite ™ (Eastman), Arkon (Trademark) (Arakawa), Norsolene (trademark), Wintack (trademark) (Cray Valley), Nevack, LX (Nevere Chemical Co.), Hikotack (trademark), Hikorez (trademark) (Kolon Chemical trademark) Rutgers NV), Quintone (TM) (Zeon), Escorez (TM) (Exoxide Mobile Chemical), Nures (TM), and H Products available in Rez (TM) (Newport Industries) can also be used.

  Conventional tackified pressure sensitive adhesives can also be turbid in appearance, demonstrating the characteristic transparency loss found in many conventional pressure sensitive adhesive compositions. This turbidity is an indicator of limited or incomplete compatibility of the tackifier and the polymer. As is clear from the fact that the tackiness is impaired or the peel adhesion strength is reduced, the compatibility may be limited, and the adhesive properties may deteriorate with time. In some cases, the addition of a tackifier to the adhesive composition can be considered transparent and compatible. However, after removal of the solvent, after curing of the adhesive, or after time, the adhesive begins to become cloudy and may exhibit some degree of insolubility between the tackifier and the acrylic polymer.

In many embodiments, the present disclosure provides tackified adhesive compositions that overcome the problems recognized in the art. Preferably, the tackifier is selected from materials that are essentially free of any ethylenic or acetylenic unsaturated bonds. Tackifiers include but are not limited to hydrogenated rosin resins, hydrogenated and esterified rosin resins, hydrogenated terpene resins, aliphatic petroleum resins, aromatic petroleum resins, aromatic petroleum resins. Examples thereof include alicyclic petroleum-based resins obtained by addition, and the like. Preferably, the tackifier to be used is not limited, selected from Regalrez (R) tackifier (Eastman) or Arkon (TM) (Arakawa) hydrogen, such as tackifier added _{C 9} petroleum resin The Such a “hydrophobic tackifier” is used in an amount of more than zero of the tackifier, for example, 10 to 150 parts, preferably 10 to 100 parts, relative to 100 parts of the isobutylene (co) polymer. May be.

  Plasticizers may also be used in adhesive formulations to provide wetting action and / or viscosity control. These plasticizers are known in the art and include liquid or soft tackifiers, waxes, including hydrocarbon oils, liquid hydrocarbon resins, liquid polyterpenes, liquid poly (isobutylene) (Glossopal ™, etc.) And a mixture of oils. The plasticizer may be present in the pressure sensitive adhesive of the present invention in an amount of 0 to about 200 parts by weight per 100 parts by weight of the copolymer.

  The adhesive of the present invention may be coated onto various flexible and inflexible backings using conventional coating techniques to produce an adhesive-coated material. A flexible substrate is defined herein as any material conventionally utilized as a tape backing or may be any other flexible material. Examples include, but are not limited to, polypropylene, polyethylene, polyvinyl chloride, polyester (polyethylene terephthalate), polycarbonate, polymethyl (meth) acrylate (PMMA), cellulose acetate, cellulose triacetate, and ethyl cellulose. Foam backing can also be used. Examples of inflexible substrates include, but are not limited to, metals, metallized polymer films, glass and polyester coated with indium tin oxide, PMMA plates, polycarbonate plates, glass, or ceramic sheet materials. Not. The adhesive coated sheet material takes the form of any article conventionally known to utilize an adhesive composition such as a label, tape, sign, cover, sign index, display component, touch panel, etc. be able to. A flexible backing having a microreplicated surface is also contemplated.

  The composition is coated onto the substrate using conventional coating techniques tailored to suit the particular substrate. For example, these compositions can be applied to various solid substrates by methods such as roller coating, flow coating, dip coating, spin coating, spray coating, knife coating, and die coating. These various coating methods allow the composition to be placed on a substrate with variable thickness, thereby allowing the composition to be used in a wider range. The coating thickness may vary, but coating thicknesses of 2 to 500 micrometers (dry thickness), preferably about 25 to 250 micrometers are contemplated.

  In some embodiments, the adhesive composition, particularly the pressure sensitive adhesive composition, is applied as a solvent solution or dispersion, the solvent is evaporated, and the adhesive composition is crosslinked upon exposure to actinic radiation such as UV. Is done. Cross-linking of such solvent-based compositions may be performed before coating and solvent removal, but is preferably performed after that. Suitable solvents such as alkanes, ethyl acetate, toluene, and tetrahydrofuran are non-reactive with the functional groups of the copolymer components.

In other embodiments, the adhesive, such as a hot melt adhesive composition, is applied from a solvent free solution. Hot melt coating of the PSA composition eliminates the need for solvent treatment. In order to hot-melt the adhesive composition, the composition must be cross-linked prior to and during the coating process, but achieves a PSA with balanced properties (ie, peel and shear adhesion). In order to achieve this, the composition must eventually be crosslinked. In hot melt coating processes, this is usually done by exposure to high energy radiation (eg, E-beam or high intensity ultraviolet radiation). Generally, when high intensity ultraviolet radiation is used, a photoactive cross-linking species such as benzophenone is added to the composition. In general, hot melt adhesive compositions require a narrower range of molecular weight poly (isobutylene) copolymers than solution coated compositions. If too low, the cross-linked polymer has insufficient cohesive strength. If it is too high, the composition cannot be extrusion coated. In general, the molecular weight of the unmodified poly (isobutylene) copolymer is 50,000 to 5,000,000, preferably 100,000 to 300,000 (M _w ).

  Conventional hot melt adhesives have poor adhesion at temperatures above their melting points and low heat resistance that limits their use. Since conventional hot melt adhesives cannot maintain sufficient adhesion at high temperatures, they cannot be used in many applications. The composition provides a reactive hot melt adhesive that overcomes this deficiency. When the adhesive compositions are crosslinked after bonding, they provide improved heat resistance.

  The adhesive composition may be combined with a crosslinking agent and cured by actinic radiation. Suitable crosslinking agents include aldehydes such as benzaldehyde, acetaldehyde, and substituted derivatives thereof; ketones such as acetophenone, benzophenone, and substituted derivatives thereof; quinones such as benzoquinone, anthraquinone, and substituted derivatives thereof; thioxanthone For example 2-isopropylthioxanthone and 2-dodecylthioxanthone; and certain chromophore substituted vinylhalomethyl-sym-triazines such as 2,4-bis- (trichloromethyl) -6- (3 ', 4'-dimethoxyphenyl) ) -Sym-triazine, but is not limited thereto. The concentration of the cross-linking agent can be present in the range of 0.05 to 6.0, preferably 0.1 to 2 weight percent, and more preferably 0.5 to 1.5 weight percent of the polymer.

The adhesive composition has a sufficient energy (ie, wavelength range) chemical radiation source to generate free radicals upon incidence on the particular photoactive crosslinker selected for use in the composition. Can be used and cured. The preferred wavelength range for the photoactive crosslinking agent disclosed above is 400-250 nm. It is required to crosslink the adhesive film of the present invention, radiant energy of a wavelength in this preferred range, 100 to 1,500 millijoules / cm ^2, and more preferably 200 to 800 millijoules / cm ^2. Details of the photocuring process are disclosed in US Pat. Nos. 4,181,752 and 4,329,384.

  The adhesives of the present disclosure are particularly useful in producing strong bonds to low surface energy (LSE) substrates. As used herein, a low surface energy substrate is one that has a surface energy of less than about 45 dyne per cm, more typically less than about 40 dyne per cm, and most typically per cm. It has a surface energy of less than about 35 dyne. Such substrates include polypropylene, polyethylene (eg, high density polyethylene or HDPE), polystyrene, and poly (methyl methacrylate) (PMMA). Other substrates may also have low surface energy characteristics due to residues such as oil residues or coatings present on the surface of the substrate. However, even if the adhesive is well bonded to a surface with low surface energy, the present invention can be applied to substrates with high surface energy, such as other plastics, ceramics, glass, and metals. It is not limited to being bonded to a substrate having a low surface energy, as it has been found that it can bond well.

  The substrate is selected according to the specific application used. For example, the adhesive can be applied to sheet products (eg, decorative designs and reflective products), label stock, and tape backings. In addition, the adhesive can be applied directly onto a substrate such as an automotive panel or glass window so that other substrates or objects can be adhered to the panel or window.

  The adhesive can also be provided in the form of a pressure sensitive adhesive transfer tape in which at least one layer of adhesive is disposed on the release liner for subsequent application to a permanent substrate. . The adhesive can also be provided as a single or double coated tape with the adhesive disposed on a permanent backing. The backing is made of resin (eg, polypropylene such as biaxially oriented polypropylene, vinyl, polyethylene, polyester, eg, polyethylene terephthalate), non-woven fabric (eg, paper, cloth, non-woven scrim), metal foil, and foam (eg, poly Acrylic acid, polyethylene, polyurethane, neoprene) and the like. The foam is 3M Co. , Voltek, Sekisui, and various other sources. The foam can be formed as a coextruded sheet with an adhesive on one or both sides of the foam, i.e. the adhesive can be laminated. When the adhesive is laminated to the foam, it may be desirable to treat the surface to improve the adhesive's adhesion to the foam or any other type of backing. Such treatment methods are typically selected based on the nature of the adhesive and the foam or backing material and include primers and surface modifiers (eg, corona treatment, surface wear). . Additional tape configurations include those described in US Pat. No. 5,602,221 (Bennett et al.), Which is incorporated herein by reference. One skilled in the art will also recognize that other additives such as fillers, antioxidants, stabilizers, and colorants may be blended with the adhesive for beneficial properties.

  In the case of a single-sided tape, typically, the surface on the back surface side opposite to the surface on which the adhesive is disposed is covered with a suitable release material. Release materials are known and include materials such as silicone, polyethylene, polycarbamate, polyacrylic and the like. With respect to the double coated tape, another adhesive layer is disposed on the backing surface opposite to the surface on which the adhesive of the present invention is disposed. Other adhesive layers may be different from the adhesives of the present invention (eg, conventional acrylic PSAs) or similar adhesives of the present invention having the same or different formulations An agent may be used. Typically, the double coated tape is applied on a release liner.

  As used in this section, the term polymer can be a homopolymer, or a copolymer, or a mixture thereof.

Test method:
90 ° peel strength test.
Peel adhesion strength is measured using an IMASS SP-200 slip / peel tester (IMAS, Inc) at an isolation speed of 305 mm / min (12 inches / min) using the procedure described in ASTM International Standard, D3330, Method F. , Available from Accor MA) at an angle of 90 °. The test panel was prepared by wiping the panel with a tissue wetted with the corresponding solvent shown in Table 1 using strong hand pressure to wipe the panel 8-10 times. This procedure was repeated twice with a clean tissue wetted with solvent. The washed panel was dried. The adhesive tape was cut into ½ pieces measuring 1.27 cm x 20 cm (1/2 inch x 8 inches), and the pieces were cut into 2.0 kg (4.5 lb.) rubber using two passes. Rolled onto a cleaned panel with a roller. The prepared sample was stored at 23 ° C./50% RH for 24 hours before testing. Two samples were tested for each example and the average value was expressed in N / dm. The failure mode was pointed out and recorded as: COH-tackiness, i.e. the adhesive splits leaving a residue on both the tape and the test surface, ADH-adhesion, i.e. the adhesive peels cleanly from the test surface As well as 2-B (2-bond) -adhesive peeled away from the backing.

Static Shear Strength Static shear strength is ASTM International Standard, D3654, procedure at 23 ° C./50% RH (relative humidity) using 1000 g load and / or 70 ° C. using 500 g load. Evaluation was as described in A. A 1.27 cm x 15.24 cm (1/2 inch x 6 inch) tape test sample is 1.5 inches using the method for cleaning the panel and bonding the tape as described in the peel adhesion test. Adhered to a x2 inch (3.81 cm x 5.08 cm) stainless steel (SS) panel. The tape was overlapped 1.27 cm x 2.5 cm to the panel and the strip was folded to itself on the adhesive side and then refolded. The hook was hung on the second fold and secured by stapling the tape on the hook. A weight was placed on the hook and the panel was placed in a 23 ° C / 50% RH room or 70 ° C oven. The time to failure was recorded in minutes. If no breakage was observed after 10,000 minutes, the test was stopped and values> 10,000 minutes were recorded. The failure mode explained in the peel adhesion test was also pointed out.

Percent Gel Test Percent gel was determined as described in ASTM International Standard, D3616-95. Circular test specimens having a radius of 63/64 inches (2.50 cm) were die cut from polymer coated tape and cured. The specimen was placed in a 1 1/2 inch × 1 1/2 inch (3.81 cm × 3.81 cm) mesh basket. The basket containing the specimen was weighed to the nearest 0.1 mg and placed in a jar with a lid containing enough toluene to cover the sample. After 24 hours, the basket (containing the specimen) was removed, drained and placed in an oven at 120 ° C. for 30 minutes. The percent gel was determined by calculating the weight percent of the remaining unextracted portion relative to the original sample. A disk of uncoated polyester backing material of the same size as the specimen was die cut and weighed. The formula used for percent gel determination is shown below.

  Percent gel (wt%) = ((unextracted sample weight after extraction-uncoated polyester backing weight) / (original sample weight-uncoated backing weight)) x 100

Materials Used in the Examples The following materials are available from ExxonMobil Corporation (Baytown, TX).
EXXPRO 3745 copolymer-brominated poly (isobutylene-co-methylstyrene)
ESCOREZ 1310-Hydrocarbon tackifier ESCOREZ 5340-Cyclic hydrocarbon tackifier

The following materials are available from Sigma Aldrich (St. Loius, MO).
・ Benzophenone ・ Diallylamine ・ Triethylamine (TEA)
・ Tetrabutylammonium bromide (TBAB)
3,7,11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol)
Trans-3,7-dimethyl-2,6-octadien-1-ol (Geranosol)
・ 3,7-dimethyl-2,6-octadienoic acid (gelanoic acid)
・ 10-Undecenoic acid ・ 2,4-Hexadienoic acid (sorbic acid)
・ Trans, trans-2,4-hexadien-1-ol (sorbine alcohol)
・ Sodium cyanide

Other materials used-Bromobutyl rubber-Brominated poly (isobutylene-co-isoprene)-Lanxess (Frieberg, Switzerland)
Available from OPPANOL B15 polymer-polyisobutylene (intermediate MW 80 Kg / mol unfunctionalized synthetic rubber) (BASF, Florham Park NJ) GLISSSOPAL 1000-unfunctionalized polyisobutylene (low MW 1000 g / mol) BASF, Florham Park, Available from NJ • 2,4-Bis-trichloromethyl-6 (4-methoxy-phenyl) -S-triazine • Diallyl malonate (Alfa Aesar, Ward Hill, Mass.)
Lithium aluminum hydride (Alfa Aesar, Ward Hill, MA)
・ Sodium hydroxide (EMD, Gibbstown, NJ)
2-allylpent-4-en-1-ol (detailed synthesis procedure is as follows)
2-allylpent-4-enoic acid (detailed synthesis procedure is as follows)
Hostaphan® 3SAB-primed polyester film (available from Mitsubishi, Greer SC)

Preparation of 2-allylpent-4-en-1-ol

Part I: Preparation of 2-allylpent-4-enoic acid ethyl ester L. J. et al. Beckwith and G.C. According to the procedure of Mod (J. Chem. Soc. Perkin II, 1975, 1726-1733), diethyl diallyl malonate (30.0 g, 125 mmol) and sodium cyanide (12.0 g, 0 mmol) in 75 mL of dimethyl sulfoxide. .24 mol) was stirred and heated at 155 ° C. for 6 hours and then allowed to cool to room temperature. After the addition of 100 mL water, the mixture was extracted with 650 mL portions of petroleum ether. The combined petroleum ether extracts were washed once with 50 mL water, dried over potassium carbonate, filtered, and the solvent was removed under reduced pressure leaving 18.8 g of a pale yellow oil. The oil was distilled and the product was collected at a temperature of 79-82 ° C. and a pressure of 5 mm to give 14.6 g of 2-allylpent-4-enoic acid ethyl ester as a colorless oil, the structure confirmed by NMR analysis did.

Part II: Preparation of 2-allylpent-4-en-1-ol of 2-allylpent-4-enoic acid ethyl ester (prepared above, 14.5 g, 86.2 mmol) in diethyl ether (125 mL) To the stirred solution, lithium aluminum hydride (3.3 g, 87 mmol) was added slowly in several portions over 30 minutes, causing vigorous gas evolution. When the addition of lithium aluminum hydride was complete, the reaction mixture was stirred once more at room temperature and then 3.5 mL of water was added very slowly. A solution of sodium hydroxide in 7 mL of 10 weight percent water was then added followed by an additional 10 mL of water. The precipitated white solid was removed from the colorless solution by filtration. The solvent was removed from the solution under reduced pressure leaving 10.1 g of 2-allylpent-4-en-1-ol as a colorless oil, the structure of which was confirmed by NMR analysis.

Preparation of 2-allylpent-4-enoic acid

  To a stirred solution of 2-allylpent-4-enoic acid ethyl ester (prepared above, 9.0 g, 54 mmol) in 50 mL methanol and 2 mL water was added sodium hydroxide (2.5 g, 63 mmol, EMD More available) was added. The solution was stirred for 15 hours and then heated at reflux temperature for 2 hours. After the reaction mixture is cooled to room temperature, the solvent is removed under reduced pressure. To the residue was added 75 mL diethyl ether and 10 mL concentrated hydrochloric acid. The mixture was stirred at room temperature for 10 minutes, then the layers were separated and the diethyl ether layer was dried over magnesium sulfate. After filtration to remove magnesium sulfate, the solvent was removed under reduced pressure leaving 4.1 g of 2-allylpent-4-enoic acid as a colorless oil, the structure of which was confirmed by NMR analysis.

Polymer Preparation Polymer 1-Diallylamine Modified Polyisobutylene in Toluene A 3-neck round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with EXXPRO 3745 copolymer (6.17 g), diallylamine (0.37 g), TEA. (0.31 g) and toluene (55.49 g) were added. The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. Once all components were completely dissolved, the flask was heated to 105 ° C. After 5 hours, the reaction was cooled to room temperature and vacuum filtered through a fritted funnel (5 μm pore size) to remove the HBr-TEA salt formed during the reaction. The filtrate was poured into acetone to coagulate the modified polymer. The isolated polymer was washed 3 times with fresh acetone to remove residual diallylamine and TEA. The polymer was then filtered and dried in a vacuum oven for 12 hours at 50 ° C. and then cooled to room temperature.

Polymer 2—Solvent-free diallylamine-modified polyisobutylene Polymer 2 is mixed with 14 g of EXXPRO 3745 and 6 g of OPPANOL B15 polyisobutylene in a Brabender mixer at 50 ° C. using a roller blade accessory rotating at 100 rpm. It was prepared by. After mixing for 8 minutes, 1.32 g diallylamine was added dropwise to the mixture and mixed for an additional 5 minutes. Then 2 g ESCOREZ-1310 tackifier and 2.2 g GLISSSOPAL G1000 plasticizer were added and mixed for 5 minutes. The resulting mixture was removed from the mixer and cooled to room temperature.

Diallylamine modified PIB using polymer 3-bromobutyl rubber
A three-necked round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (5.0 g), diallylamine (0.28 g), TEA (0.23 g), and toluene (45.00 g). I put it in. The procedure from this point followed that described for polymer 1.

Polymer 4-farnesol modified PIB using brominated butyl rubber
A three-necked round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), farnesol (1.14 g), TBAB (0.55 g), and toluene (135.00 g). I put it in. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual farnesol and TBAB.

Synthesis of Geraniol Modified PIB Using Polymer 5-Bromobutyl Rubber A three-necked round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g) and geraneol (0.79 g). , TBAB (0.55 g), and toluene (135.00 g). The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual geraniol and TBAB.

Polymer 6-gelatin modified PIB using bromobutyl rubber
A three-neck round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), gellanic acid (0.86 g), TBAB (0.55 g), and toluene (135.00 g). Put. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual gellanic acid and TBAB.

10-Undecenoic acid modified PIB using polymer 7-bromobutyl rubber
A three neck round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), 10-undecenoic acid (0.95 g), TBAB (0.55 g), and toluene (135. 00 g). The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual 10-undecenoic acid and TBAB.

Trans, trans-2,4-hexadien-1-ol modified PIB using polymer 8-bromobutyl rubber
A three-necked round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), trans, trans-2,4-hexadien-1-ol (0.40 g), TBAB (0 .55 g) and toluene (135.00 g) were added. The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual trans, trans-2,4-hexadien-1-ol and TBAB.

2,4-hexadienoic acid modified PIB using polymer 9-bromobutyl rubber
A three-neck round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), 2,4-hexadienoic acid (0.46 g), TBAB (0.55 g), and toluene ( 135.00 g) was added. The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual 2,4-hexadienoic acid and TBAB.

2-Allylpent-4-en-1-ol modified PIB using polymer 10-bromobutyl rubber
A three-neck round bottom flask equipped with a reflux condenser, a thermometer, and a nitrogen inlet was charged with bromobutyl rubber (15.0 g), 2-allylpent-4-en-1-ol (0.52 g), TBAB (0.55 g). ) And toluene (135.00 g). The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual 2-allylpent-4-en-1-ol and TBAB.

2-allylpent-4-enoic acid modified PIB using polymer 11-bromobutyl rubber
A three-neck round bottom flask equipped with a reflux condenser, thermometer, and nitrogen inlet was charged with bromobutyl rubber (15.0 g), 2-allylpent-4-enoic acid (0.58 g), TBAB (0.55 g), and Toluene (135.00 g) was added. The contents of the flask were stirred with a magnetic stir bar at room temperature under nitrogen. The procedure from this point followed that described for polymer 1 except that acetone was used to remove residual 2-allylpent-4-enoic acid and TBAB.

Examples 1-4 and control compositions C1-C4
The adhesive composition consists of 100 parts polymer 1 in a 100 mL bottle, 400 parts toluene, 0.2 pph (parts per 100 parts polymer) photocrosslinker (2,4-bis-trichloromethyl-6 (4-methoxy-phenyl) -S-triazine) and various amounts of tackifier (ESCOREZ 1310) and plasticizer (GLISSSOPAL 1000) shown in Table 3 in pph. The jar was capped and mixed overnight on a roller mill. The resulting composition was placed on a 6 inch x 25 inch (15.2 cm x 63.5 cm) strip of polyester film backing (Hostaphan® 3SAB) with a wet thickness of about 15 mils (0.381 mm). ) Was knife coated. The coated film was dried in an oven set at 70 ° C. for 20 minutes to provide a tape having an adhesive coating thickness of 2 mils (0.051 mm). The coated tape was cured by irradiation with UV light (400 mJ / cm ² , UVB) using a UV processor (Fusion UV System, Inc., Gaithersburg, MD).

  A control composition having the same amount and type of tackifier in toluene and a plasticizer with unmodified EXXPRO 3745 was also prepared (C1, C2, C3, C4) and coated onto tape. No crosslinker was added. The tape was conditioned at 23 ° C. and 50% RH before testing for 90 ° peel adhesion on Santoprene ™ and shear strength on stainless steel. The test results are shown in Table 2.

Examples 5-6 Effect of UV Exposure on Properties Tapes were prepared as described in Example 3 except that the amount of exposure to UV energy was varied to provide different crosslink densities. The adhesive properties are shown in Table 3.

(Examples 7 to 9)
The adhesive compositions of Examples 7-8 were different except that different amounts of unfunctionalized, intermediate molecular weight polyisobutylene (OPPANOL B15) shown in Table 5 were added along with polymer 1 and the amount of photocrosslinker was changed. Prepared as described in Example 3 and coated to tape. The amount of ESCOREZ 1310 tackifier and Glossopal 1000 plasticizer were both maintained at 10 pph. The total amount of polyisobutylene in the system remained at 100 parts, but the amount of modified and unmodified polyisobutylene was varied and shown in Table 4 in parts (parts per 100 parts polymer).

  For Example 9, an adhesive composition was prepared as described in Example 7 except that polymer 2 was dissolved in 400 parts of toluene to form a 20% solid solution solution and taped. And coated. 15 g of the solution was then placed in a glass vial and mixed with 3.5 mg of crosslinker (2,4-bis-trichloromethyl-6 (4-methoxy-phenyl) -S-triazine) and coated. The test results of Examples 7 to 9 are shown in Table 4.

^＊ポリマー２とともに調製

^* Prepared with polymer 2

(Examples 10 to 11)
The adhesive tape was prepared as described in Example 8, except that the amount of UV exposure was changed to change the crosslink density of the adhesive. The tape was tested for shear at room temperature and 70 ° C., and 90 ° peel adhesive properties on various substrates. The test results are shown in Tables 5 and 6, respectively.

(Example 12)
The adhesive composition and tape made from the composition were prepared as described in Example 3 using Polymer 3. The tapes were tested for shear strength at 23 ° C., 50% RH, and 90 ° peel adhesive on various substrates. The test results are shown in Table 7.

(Examples 13 to 15)
The adhesive compositions and tapes of Examples 13-15 were prepared as described in Examples 4, 7, and 8, respectively, except that the modified PIB was Polymer 4. The test results for shear at 23 ° C. and 50% RH and peel adhesion are shown in Table 8.

(Examples 16 to 18)
The adhesive compositions and tapes of Examples 16-18 were prepared as described in Examples 13-15, respectively, except that the modified PIB was Polymer 5. The test results for shear at 23 ° C. and 50% RH and peel adhesion are shown in Table 9.

(Examples 19 to 21)
The adhesive compositions and tapes of Examples 19-21 were prepared as described in Examples 13-15, respectively, except that the modified PIB was Polymer 6. The test results for shear at 23 ° C. and 50% RH and peel adhesion are shown in Table 10.

(Examples 22 to 24)
The adhesive compositions and tapes of Examples 22-24 were prepared as described in Examples 13-15, respectively, except that the modified PIB was Polymer 7. Table 11 shows the test results regarding shear at 23 ° C. and 50% RH, and peel adhesion.

Example (25-26)
The adhesive compositions and tapes of Examples 25-26 were prepared using polymer 8 as described in Table 12. Table 13 shows the test results regarding shear at 23 ° C., 50% RH, and peel adhesion.

(Examples 27 to 28)
The adhesive compositions and tapes of Examples 27-28 were prepared as described in Examples 25-26, respectively, except that the modified PIB was Polymer 9. The test results for shear at 23 ° C., 50% RH, and peel adhesion are shown in Table 14.

(Examples 29 to 30)
PIB was polymer 10. The test results for shear at 23 ° C., 50% RH, and peel adhesion are shown in Table 15.

(Examples 31-32)
The adhesive compositions and tapes of Examples 31-32 were prepared as described in Examples 25-26, respectively, except that the modified PIB was Polymer 11. The test results for shear at 23 ° C., 50% RH, and peel adhesion are shown in Table 16.

(Examples 33 to 50)
The gel contents of Polymers 1 and 2-11 were determined by using only the polymer and crosslinker without using a tackifier or plasticizer. Each composition was prepared by dissolving 100 parts of polymer in 400 parts of toluene and adding the amount of crosslinker indicated by pph. Crosslinker I was 2,4-bis-trichloromethyl-6 (4-methoxy-phenyl) -S-triazine and crosslinker II was benzophenone. Each composition was coated to the indicated sample thickness and dried in an oven set at 70 ° C. The composition was cured with the amount of UV energy shown in Table 17. The gel content of each cured composition was determined as described in the test method.

  The invention is illustrated with the following embodiments.

Embodiments of the invention:
1. An adhesive composition comprising: a) an isobutylene copolymer having a pendant free radical polymerizable ethylenically unsaturated group; b) a tackifier; and c) a photocrosslinker.

  2. The adhesive composition of embodiment 1, comprising more than 0% by weight but less than 20% by weight polymerized monomer units having pendant free radical polymerizable ethylenically unsaturated groups.

  3. The adhesive composition according to embodiment 2, wherein the polymerization monomer unit having the pendant free radical polymerizable ethylenically unsaturated group is an isoprene monomer unit.

  4). The adhesive composition according to embodiment 1, wherein the free radical polymerizable ethylenically unsaturated group is an alkenyl group.

（式中、Ｑは二価連結基であり、Ｒ^７はＨ又はＣＨ_３であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基である）ある、実施形態２に記載の接着剤組成物。 5. The monomer unit having the pendant free radical polymerizable ethylenically unsaturated group has the formula:

The adhesive composition according to embodiment 2, wherein Q is a divalent linking group, R ⁷ is H or CH ₃ , and Z is a pendant free radical polymerizable ethylenically unsaturated group. .

  6. The adhesive composition according to any one of embodiments 1 to 5, comprising more than 0 to 150 parts by weight of the tackifier per 100 parts by weight of the copolymer.

  7. The adhesive composition according to any one of embodiments 1 to 5, comprising 10 to 100 parts by weight of the tackifier per 100 parts by weight of the copolymer.

  8). Embodiment 8. The adhesive composition according to any one of embodiments 1 to 7, wherein the photocrosslinker is selected from aldehydes, ketones, quinones, thioxanthones, and chromophore-substituted vinylhalomethyl-sym-triazine photocrosslinkers. .

（式中、ａは少なくとも２０であり、ｂ及びｃのうちの少なくとも１つは少なくとも１であり、
Ｑは二価連結基であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基である）である、実施形態１〜８のいずれか１つに記載の接着剤組成物。 9. The copolymer has the formula:

Wherein a is at least 20, at least one of b and c is at least 1,
Embodiment 9 The adhesive composition according to any one of Embodiments 1 to 8, wherein Q is a divalent linking group and Z is a pendant free radical polymerizable ethylenically unsaturated group.

（式中、ａ及びｄは少なくとも１であり、Ｑは多価連結基であり、Ｒ^７はＨ又はＣＨ_３であり、Ｚはペンダントフリーラジカル重合性エチレン性不飽和基である）である、実施形態１〜９のいずれか１つに記載の接着剤組成物。 10. The copolymer has the formula:

Wherein a and d are at least 1, Q is a multivalent linking group, R ⁷ is H or CH ₃ , and Z is a pendant free radical polymerizable ethylenically unsaturated group. The adhesive composition according to any one of Embodiments 1 to 9.

  11. Embodiment 11. The adhesive composition of any one of embodiments 1-10, wherein the copolymer has a molecular weight (Mw) of 50,000 to 5,000,000.

  12 Embodiment 6. The adhesive composition according to embodiment 5, wherein Z is an alkenyl-containing group.

（Ｒ^１は多価アルキレン又はアリーレンであり、Ｘ^１は−Ｏ−、−Ｏ_２Ｃ−、−ＮＲ^４−（式中、Ｒ^４はＨ又はＣ_１〜Ｃ_４アルキルである）、又は−Ｒ^２−Ｃ（Ｒ^５）＝ＣＲ^５ _２であり、Ｒ^２は多価アルキレン又はアリーレンであり、各Ｒ^５は、Ｈ又はＣ_１〜Ｃ_４アルキルから独立して選択され、前記Ｒ^５基のうちのいずれか２つは、一緒になって炭素環を形成し得、ｒは１〜５であり、ｑは１又は２である）である、実施形態５に記載の接着剤組成物。 13. The -Q-Z moiety has the formula:

(R ¹ is a polyvalent alkylene or arylene, X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C ₁ -C ₄ alkyl), or — R ² -C ^(R 5) = a ^CR _{5 2,} ^{R 2} is a polyvalent alkylene or arylene, each ^{R 5} is independently selected from H or _C 1 -C ₄ alkyl, the ^{R 5} groups Any two of them can form a carbocycle together, r is 1-5 and q is 1 or 2.) The adhesive composition of embodiment 5.

14 QZ is the formula:
^{-R 1 -X 1 -R 2 - (} - CH = CH 2) q
(Wherein R ¹ is a polyvalent alkylene or arylene, and X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C ₁ -C ₄ alkyl) , or ^-R 2 ^-C (R 5) = a ^CR _{5 2,} ^{R 2} is a polyvalent arylene or alkylene, q is 1 or 2, ^{R 5} are independently H or _C 1 -C ₄ 6. The adhesive composition of embodiment 5, wherein the adhesive composition is alkyl).

15. The adhesive composition according to embodiment 14, wherein R ¹ is divalent alkylene or arylene and R ² is divalent alkylene.

である、実施形態５に記載の接着剤組成物。 16. -Q-Z is

The adhesive composition according to embodiment 5, wherein

  17. Embodiment 6. The adhesive composition according to embodiment 5, wherein QZ is derived from terpene alcohol or acid.

  18. 18. The adhesive composition according to any one of embodiments 1-17, which is crosslinked.

  19. An adhesive article comprising the crosslinked adhesive composition of embodiment 18 on a backing.

  20. The adhesive composition according to any one of Embodiments 1 to 17, wherein the adhesive is a hot melt adhesive.

  21. The adhesive according to any of embodiments 1-17, wherein said isobutylene copolymer having pendant free radical polymerizable ethylenically unsaturated groups is prepared by nucleophilic substitution of a halogenated isobutylene copolymer with a nucleophilic ethylenically unsaturated compound. Agent composition.

（式中、
Ｘ^１は−Ｏ−、−Ｏ_２Ｃ−、−ＮＲ^４−（式中、Ｒ^４はＨ又はＣ_１〜Ｃ_４アルキルである）、又は−Ｒ^２−Ｃ（Ｒ^５）＝ＣＲ^５ _２であり、Ｒ^２は多価飽和又は不飽和アルキレン又はアリーレンであり、各Ｒ^５は、Ｈ又はＣ_１〜Ｃ_４アルキルから独立して選択され、前記Ｒ^５基のうちのいずれか２つは、一緒になって炭素環を形成し得る）である、実施形態２１に記載の接着剤組成物。 22. The nucleophilic ethylenically unsaturated compound has the formula:

(Where
X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C _{1 to} C ₄ alkyl), or —R ² —C (R ⁵ ) ═CR ⁵ _2. Wherein R ² is a polyvalent saturated or unsaturated alkylene or arylene, each R ⁵ is independently selected from H or C ₁ -C ₄ alkyl, and any two of the R ⁵ groups are The adhesive composition according to embodiment 21, which can together form a carbocycle).

  23. The adhesive composition according to embodiment 22, wherein the nucleophilic ethylenically unsaturated compound is terpene alcohol or terpenic acid.

Claims (6)

an isobutylene copolymer having a pendant free radical polymerizable ethylenically unsaturated group, b) a tackifier, and c) a photocrosslinker,
The copolymer has the formula:

Wherein a is at least 20, at least one of b and c is at least 1, Q is a divalent linking group, and Z is a pendant free radical polymerizable ethylenically unsaturated group. An adhesive composition. The adhesive composition of claim 1, wherein the copolymer comprises greater than 0 wt% but less than 20 wt% polymerized monomer units having pendant free radical polymerizable ethylenically unsaturated groups.   The adhesive composition according to claim 1, comprising more than 0 to 150 parts by weight of the tackifier per 100 parts by weight of the copolymer. The -Q-Z moiety has the formula:

(Wherein R ¹ is a polyvalent alkylene or arylene, and X ¹ is —O—, —O ₂ C—, —NR ⁴ — (wherein R ⁴ is H or C ₁ -C ₄ alkyl) , or ^-R 2 ^-C (R 5) = a ^CR _{5 2,} ^{R 2} is a polyvalent alkylene or arylene, each ^{R 5} is independently selected from H or _C 1 -C ₄ alkyl, wherein The adhesive of claim 1 , wherein any two of the R ⁵ groups can be taken together to form a carbocycle, wherein r is 1-5 and q is 1 or 2. Composition.   The adhesive composition according to claim 1, which is crosslinked. The adhesive composition of claim 1, wherein the isobutylene copolymer having pendant free radical polymerizable ethylenically unsaturated groups is prepared by nucleophilic substitution of a halogenated isobutylene copolymer with a nucleophilic ethylenically unsaturated compound.